KR20210015916A - Crosslinkable compounds based on organyloxy group-containing organopolysiloxanes - Google Patents

Abstract

The present invention is a crosslinkable composition containing an organyloxy group and based on an organopolysiloxane, in particular a crosslinkable composition having a low viscosity and having self-smooth properties, a method for its preparation, and its use, in particular as a coating or liquid application film. Regarding the use, the crosslinkable composition,
(A) Organopolysiloxane containing an organyloxy group and composed of units of the following formula (I):
RaR ¹ _b (OR ² ) _c SiO _(4-abc)/2 (I),
(B) the organosilicon compound of the following formula (II) and/or a partial hydrolyzate thereof:
(R ⁴ O) _d SiR ³ _(4-d) (II),
(C) an organosilicon compound containing basic nitrogen and having the following formula (III) and/or a partial hydrolyzate thereof:
(R ⁶ O) _e SiR ⁵ _(4-e) (III),
And
(D) the organosilicon compound of the following formula (IV) and/or a partial hydrolyzate thereof:
(R ⁸ O) _h SiR ⁷ _(4-h) (IV),
Wherein the radicals and indices have the definition set forth in claim 1.

Description

Crosslinkable compounds based on organyloxy group-containing organopolysiloxanes

The present invention is a crosslinkable composition containing an organyloxy group and based on an organopolysiloxane, in particular a crosslinkable composition having a low viscosity and having self-smooth properties, a method for its preparation, and its use, in particular as a coating or liquid application film. It is about the use.

A single component (RTV-1) sealant that can be stored by excluding moisture, but is vulcanized with an elastomer when moisture is allowed, has long been known. Such products can be used in large quantities as sealants for connecting joints or facade joints, for example in the construction industry, or applied as elastic coatings. These mixtures are based on polymers terminated with silyl groups, for example carrying reactive substituents such as OH groups, or hydrolyzable groups such as alkoxy groups. In addition, these sealants may include fillers, plasticizers, crosslinkers, catalysts, and additives. In this respect, reference may be made, for example, to EP-A 763557, EP-A 1865029 and EP-A 1042400. Compared to other neutral systems, the alkoxy-RTV-1 composition is preferred because of its neutral, odorless crosslinking and very good adhesion to different substrates. This alkoxy-RTV-1 composition is important not only for a paste-type sealant, but also as a reactive coating material. Such formulations can usually be sprayed using brushes and rollers, or should be able to be sprayed, for example via an airless spray. The problem here is to combine good processing quality and viscosity with a guarantee of strong hardening and sufficient mechanical properties. The simplest way to adjust the viscosity is to add a solvent. However, solvents are not desired because of their flammability or VOCs. Low viscosity polymers are generally brittle, resulting in a fragile composition, or must be recompensated using reinforcing fillers that are rheologically active. A compromise is, for example, reactive diluents such as functional alkoxysilanes, but these generally very sharply affect the cure or cause embrittlement in the vulcanisate.

Now the object is to provide a crosslinkable composition based on organopolysiloxane containing organyloxy groups, which can realize extremely low and easily adjusted viscosity at the same time with strong curing and excellent mechanical properties without the need for solvents or non-reactive plasticizers. Was to do.

The subject of the present invention is

(A) Organopolysiloxane containing an organyloxy group and composed of units of the following formula (I):

R _a R ¹ _b (OR ² ) _c SiO _(4-abc)/2 (I)

(Wherein, R may be the same or different and represents a monovalent, SiC-bonded, optionally substituted hydrocarbyl radical without aliphatic carbon-carbon multiple bonds,

R ¹ may be the same or different and represents a monovalent, SiC-bonded, optionally substituted hydrocarbyl radical having aliphatic carbon-carbon multiple bonds,

R ² may be the same or different and represent a monovalent, optionally substituted hydrocarbyl radical, which may be interrupted by an oxygen atom,

a is 0, 1, 2 or 3,

b is 0 or 1,

c is 0, 1, 2 or 3,

However, in formula (I), the sum of a+b+c is 3 or less, and c is not 0 in one or more units),

(B) the organosilicon compound of the following formula (II) and/or a partial hydrolyzate thereof:

(R ⁴ O) _d SiR ³ _(4-d) (II)

(Wherein, R ³ may be the same or different and optionally have 1 to 7 carbon atoms substituted by an ether group, an ester group, a (poly) glycol radical or a triorganyloxysilyl group, a monovalent, SiC- Represents a bonded, aliphatic hydrocarbyl radical or an aromatic radical,

R ⁴ may be the same or different and represent a hydrogen atom or represent a monovalent, optionally substituted hydrocarbyl radical, which may be interrupted by an oxygen atom,

d is 2, 3 or 4, preferably 3 or 4, more preferably 3),

(C) an organosilicon compound containing basic nitrogen and having the following formula (III) and/or a partial hydrolyzate thereof:

(R ⁶ O) _e SiR ⁵ _(4-e) (III)

(Wherein, R ⁵ may be the same or different and represent a monovalent, SiC-bonded radical containing a basic nitrogen,

R ⁶ may be the same or different and represent a hydrogen atom or represent a monovalent, optionally substituted hydrocarbyl radical, which may be interrupted by an oxygen atom,

e is 2 or 3, preferably 3), and

(D) the organosilicon compound of the following formula (IV) and/or a partial hydrolyzate thereof:

(R ⁸ O) _h SiR ⁷ _(4-h) (IV)

(In the formula, R ⁷ may be the same or different, optionally substituted by an ether group, an ester group, a (poly) glycol radical or a triorganyloxysilyl group, and having 8 or more carbon atoms, a monovalent, SiC-bond Represents an aliphatic hydrocarbyl radical,

R ⁸ may be the same or different and represent a hydrogen atom or represent a monovalent, optionally substituted hydrocarbyl radical, which may be interrupted by an oxygen atom,

h is 2 or 3, preferably 3),

It is for a crosslinkable composition comprising a.

In the context of the present invention, the term "organopolysiloxane" is intended to encompass polymerizable, oligomeric and dimeric siloxanes.

The crosslinkable composition is preferably a composition that can be crosslinked by a condensation reaction.

In the context of the present invention, what the "condensation reaction" refers to is also intended to encompass any preceding hydrolysis step.

Examples of radicals R are alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl , tert-pentyl radical; Hexyl radicals such as the n-hexyl radical; Heptyl radicals such as the n-heptyl radical; Octyl radicals such as n-octyl radicals and isooctyl radicals such as 2,2,4-trimethylpentyl radicals; Nonyl radicals such as the n-nonyl radical; Decyl radicals such as the n-decyl radical; Dodecyl radicals such as the n-dodecyl radical; Octadecyl radicals such as the n-octadecyl radical; Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl radical and methylcyclohexyl radical; Aryl radicals such as phenyl, naphthyl, anthryl, and phenanthryl radicals; Alkaryl radicals such as o-, m- and p-tolyl radicals; Xylyl radical and ethylphenyl radical; And aralkyl radicals such as benzyl radicals, α- and β-phenylethyl radicals.

Examples of substituted radicals R are methoxyethyl, ethoxyethyl, ethoxyethoxyethyl radicals or polyoxyalkyl radicals such as polyethylene glycol or polypropylene glycol radicals.

The radical R is preferably free of aliphatic carbon-carbon multiple bonds and is optionally substituted by a halogen atom, an amino group, an ether group, an ester group, an epoxy group, a mercapto group, a cyano group or a (poly) glycol radical, and 1 to 18 carbons. A monovalent hydrocarbyl radical having an atom, more preferably a monovalent hydrocarbyl radical having 1 to 12 carbon atoms without aliphatic carbon-carbon multiple bonds, and more particularly a methyl radical. .

Examples of the radical R ¹ are alkenyl radicals, such as linear or branched 1-alkenyl radicals, such as vinyl radicals and 1-propenyl radicals, and also 2-propenyl radicals.

The radical R ¹ preferably has an aliphatic carbon-carbon multiple bond and is optionally substituted by a halogen atom, an amino group, an ether group, an ester group, an epoxy group, a mercapto group, a cyano group or a (poly) glycol radical, and 1 to 18 Monovalent hydrocarbyl radicals having carbon atoms, more preferably monovalent hydrocarbyl radicals having 1 to 12 carbon atoms and having aliphatic carbon-carbon multiple bonds, and more particularly vinyl radicals do.

Examples of radicals R ² are the monovalent radicals described for R and R ¹ .

The radical R ² comprises a monovalent, optionally substituted hydrocarbyl radical, preferably having 1 to 12 carbon atoms, which may be interposed by an oxygen atom, more preferably 1 to 6 Alkyl radicals having carbon atoms, and more particularly methyl or ethyl radicals, and very preferably methyl radicals.

The organopolysiloxane (A) used according to the invention is preferably composed of units of formula (I) in which b and c are not zero in one or more units.

The organopolysiloxane (A) used according to the invention is preferably a substantially linear, organyloxy-terminated organopolysiloxane, more preferably an organopolysiloxane of formula (V):

(OR ² ) _3-f R ¹ _f Si-(SiR ₂ -O) _g -SiR ¹ _f (OR ² ) _3-f (V)

(In the formula, R, R ¹ and R ² may each be the same or different, and have one of the definitions described above,

g is 30 to 5000,

f is 0, 1 or 2, preferably 1,

However, in equation (V), f is not 0 in one or more units)

Although not specified in formula (V), the organopolysiloxane (A) of formula (V) used according to the invention, due to their preparation, has a small proportion of branching, preferably up to 500 ppm of all Si units It may contain as, and more particularly may not contain.

Although not specified in formulas (I) and (V), the organopolysiloxanes (A) used according to the invention, due to their preparation, have a small proportion of hydroxyl groups, preferably the maximum of all Si-bonded radicals. It may contain less than 5%.

Preferred examples of organopolysiloxane (A) are,

(MeO) ₂ MeSiO[SiMe ₂ O] _200-2000 SiMe(OMe) ₂ ,

(MeO) ₂ MeSiO[SiMe ₂ O] _200-2000 SiVi(OMe) ₂ ,

(MeO) ₂ ViSiO[SiMe ₂ O] _200-2000 SiVi(OMe) ₂ ,

(MeO) ₂ MeSiO [SiMe ₂ O] _200-2000 SiViMe (OMe),

(MeO)ViMeSiO[SiMe ₂ O] _200-2000 SiViMe(OMe) or

(MeO)ViMeSiO[SiMe ₂ O] _200-2000 SiVi(OMe) _{2 ,}

Here, (MeO) ₂ MeSiO[SiMe ₂ O] _200-2000 SiVi(OMe) ₂ or

(MeO) ₂ ViSiO[SiMe ₂ O] _200-2000 SiVi(OMe) ₂ is particularly preferred,

More particularly (MeO) ₂ ViSiO[SiMe ₂ O] _200-2000 SiVi(OMe) ₂ .

The organopolysiloxane (A) used according to the invention has in each case a viscosity of preferably 1000 to 10 ⁶ mPas, more preferably 1000 to 10 ⁵ mPas, in particular 1000 to 50,000 mPas at 25°C.

The organopolysiloxane (A) is a commercially available product and/or can be prepared and isolated prior to compounding by methods common in silicone chemistry.

Examples of radicals R ³ are the monovalent radicals described for R and R ¹ .

The radical R ³ is preferably a monovalent aliphatic hydrocarbyl radical having 1 to 7 carbon atoms, optionally substituted by an ether group, an ester group, a (poly) glycol radical or a triorganyloxysilyl group, or an ether group , An ester group, an aromatic hydrocarbyl radical optionally substituted by a (poly) glycol radical or a triorganyloxysilyl group, more preferably an alkyl radical having 1 to 7 carbon atoms or 1 to 7 Alkenyl radicals having carbon atoms or aromatic hydrocarbyl radicals, more particularly methyl radicals and vinyl radicals.

Examples of radicals R ⁴ are hydrogen atoms and are monovalent radicals described for R and R ¹ .

The radical R ⁴ preferably comprises a monovalent, optionally substituted hydrocarbyl radical having 1 to 12 carbon atoms, which may be interrupted by an oxygen atom, more preferably 1 to 6 carbon atoms Alkyl radicals, more particularly methyl or ethyl radicals, and very preferably ethyl radicals.

The organosilicone compound (B) used in the composition of the present invention is preferably a silane having at least one methoxy or ethoxy radical and/or a partial hydrolyzate thereof, more preferably tetraethoxysilane, methyl Trimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane or 1,2 -Bis(triethoxysilyl)ethane and/or partial hydrolyzates thereof, more particularly tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane and/or partial hydrolyzates thereof , Very preferably methyltrimethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane and/or partial hydrolyzate thereof, particularly preferably vinyltriethoxysilane and/or partial hydrolyzate thereof.

The partial hydrolyzate (B) is a partial homohydrolysate, i.e. a partial hydrolyzate of one organosilicone compound of formula (II), and also a partial cohydrolysate, i.e., two or more different formulas. It may be a partial hydrolyzate of the organosilicon compound of (II).

When the compound (B) used in the composition of the present invention is a partial hydrolyzate of an organosilicon compound of formula (II), those having 10 or less silicon atoms are preferred.

The crosslinking agent (B) optionally used in the composition of the present invention is a commercially available product and/or can be prepared by a method known in silicone chemistry.

The composition of the present invention is in each case based on 100 parts by weight of organopolysiloxane (A), preferably 0.5 to 15.0 parts by weight, more preferably 0.5 to 10.0 parts by weight, more particularly 1.0 to 5.0 parts by weight of component (B ).

Examples of radicals R ⁵ include the formula H ₂ NCH ₂ -, H ₂ N(CH ₂ ) ₂ -, H ₂ N(CH ₂ ) ₃ -, H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₂ -, H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₃ -, H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₂ NH(CH ₂ ) ₃ -, H ₃ CNH(CH ₂ ) ₃ -, C ₂ H ₅ NH(CH ₂ ) ₃ -,

H ₃ CNH(CH ₂ ) ₂ -, C ₂ H ₅ NH(CH ₂ ) ₂ -, H ₂ N(CH ₂ ) ₄ -, H ₂ N(CH ₂ ) ₅ -, H(NHCH ₂ CH ₂ ) ₃ -, C ₄ H ₉ NH(CH ₂ ) ₂ NH(CH ₂ ) ₂ -, Cyclo-C ₆ H ₁₁ NH(CH ₂ ) ₃ -, Cyclo-C ₆ H ₁₁ NH(CH ₂ ) ₂ -, (CH ₃ ) ₂ N(CH ₂ ) ₃ -, (CH ₃ ) ₂ N(CH ₂ ) ₂ -, (C ₂ H ₅ ) ₂ N(CH ₂ ) ₃ -and (C ₂ H ₅ ) ₂ N(CH ₂ ) ₂ -is a radical of.

The radical R ⁵ is preferably H ₂ N(CH ₂ ) ₃ -, H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₃ -, H ₃ CNH(CH ₂ ) ₃ -, C ₂ H ₅ NH(CH ₂ ) ₃ -or cyclo-C ₆ H ₁₁ NH(CH ₂ ) ₃ -radicals, more particularly H ₂ N(CH ₂ ) ₂ NH(CH ₂ ) ₃ -radicals.

Examples of the radical R ⁶ are a hydrogen atom, and are also examples described for the radical R ² .

The radical R ⁶ preferably comprises a monovalent, optionally substituted hydrocarbyl radical having 1 to 12 carbon atoms, which may be interrupted by an oxygen atom, more preferably 1 to 6 carbon atoms Alkyl radicals, and more particularly methyl or ethyl radicals.

The organosilicon compound (C) is preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-( 2-Aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane , N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, or N-phenyl-3-aminopropyl N- of methyldiethoxysilane, or 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane or 3-aminopropylmethyldiethoxysilane or a partial hydrolyzate thereof Alkyl or N,N-dialkyl derivatives, wherein the N-alkyl radicals described are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl or various branched Or an unbranched pentyl or hexyl radical.

Compound (C) is more preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane or N-(2-amino Ethyl)-3-aminopropyltriethoxysilane, more particularly N-(2-aminoethyl)-3-aminopropyltrimethoxysilane or N-(2-aminoethyl)-3-aminopropyltriethoxy It is silane.

The compound (C) used in the composition of the present invention is a commercially available product and/or can be prepared by a method known in silicone chemistry.

The composition of the present invention, in each case, based on 100 parts by weight of organopolysiloxane (A), preferably 0.5 to 15.0 parts by weight, more preferably 0.5 to 10.0 parts by weight, more particularly 0.5 to 5.0 parts by weight of the component ( C).

In the composition of the present invention, the weight ratio of component (B) to component (C) is preferably in the range of 2:1 to 1:2, more preferably in the range of 3:2 to 2:3.

Examples of radicals R ⁷ are monovalent aliphatic radicals specified for R and R ¹ having 8 or more carbon atoms.

The radical R ⁷ preferably contains a monovalent aliphatic hydrocarbyl radical having 8 or more carbon atoms and optionally substituted by an ether group, an ester group, a (poly) glycol radical or a triorganyloxysilyl group, more preferably Preferably, an ether group, an ester group, a (poly) glycol radical or a triorganyloxysilyl group, optionally substituted with a monovalent aliphatic hydrocarbyl radical having 8 to 18 carbon atoms, more particularly 8 Aliphatic hydrocarbyl radicals having from to 16 carbon atoms, very particularly preferably alkyl radicals having from 8 to 16 carbon atoms.

Examples of radicals R ⁸ are hydrogen atoms and monovalent radicals described for R and R ¹ .

The radical R ⁸ preferably comprises a monovalent, optionally substituted hydrocarbyl radical having 1 to 12 carbon atoms, which may be interrupted by an oxygen atom, more preferably 1 to 6 carbon atoms Alkyl radicals, more particularly methyl or ethyl radicals, and very preferably ethyl radicals.

The organosilicon compound (D) preferably has at least one radical R ⁸ having at least 2 carbon atoms.

The organosilicone compound (D) used in the composition of the present invention is preferably hexadecyltrimethoxysilane, hexadecyl-triecoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, Isooctyltrimethoxysilane or isooctyltriethoxysilane and/or a partial hydrolyzate thereof, and more preferably n-octyltriethoxysilane or isooctyltriethoxysilane.

The partial hydrolyzate (D) is a partial homohydrolyzate, i.e. a partial hydrolyzate of one organosilicone compound of formula (IV), and also a partial cohydrolyzate, i.e., two or more different organos of formula (IV). It may be a partial hydrolyzate of a silicone compound.

When the compound (D) used in the composition of the present invention is a partial hydrolyzate of an organosilicon compound of formula (IV), those having 10 or less silicon atoms are preferred.

The compound (D) optionally used in the composition of the present invention is a commercially available product and/or can be prepared by a method known in silicone chemistry.

The composition of the present invention, in each case, based on 100 parts by weight of organopolysiloxane (A), preferably in an amount of 5 to 100 parts by weight, more preferably 10 to 80 parts by weight, more particularly 20 to 50 parts by weight of the component ( D).

In addition to components (A), (B), (C) and (D), the compositions of the present invention may now contain all additional components that have been used to date in compositions that can be crosslinked by condensation reactions; Examples of such additional components include (E) fillers, (F) catalysts, (G) stabilizers, (H) additives and (J) plasticizers.

Examples of fillers (E) are unreinforced fillers, which are fillers having a BET surface area of 50 m ² /g or less, such as uncoated calcium carbonate, coated calcium carbonate, quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolite. , Metal oxide powders such as aluminum, titanium, iron or zinc oxides and/or mixed oxides thereof, barium sulfate, gypsum, silicon nitride, silicon carbide, boron nitride, or glass powders and polymeric powders such as It is a polyacrylonitrile powder. Examples of reinforcing fillers, which are fillers with a BET surface area of more than 50 m ² /g, are pyrogenically prepared silica, precipitated silica, carbon blacks such as furnace black and acetylene black, and It is a mixed silicon-aluminum oxide with high BET surface area. Furthermore, it is also possible to use fibrous fillers such as asbestos, or polymeric fibers. The mentioned fillers may have been hydrophobized, for example, by treatment with organosilanes and/or organosiloxanes, stearic acid derivatives, or by etherification of hydroxyl groups to alkoxy groups.

When fillers (E) are used, these are preferably untreated calcium carbonate, hydrophilic, pyrogenically prepared silica, or hydrophobic, pyrogenically prepared silica.

When the composition of the present invention comprises an actual filler (E), in each case, based on 100 parts by weight of organopolysiloxane (A), preferably 10 to 500 parts by weight, more preferably 10 to 200 parts by weight, very preferred It is related in an amount of 50 to 200 parts by weight.

As catalyst (F) it is also possible to use all curing accelerators that have been used to date in compositions that can be crosslinked by condensation reactions. Examples of the optionally used catalyst (F) include organotine compounds such as di-n-butyltin dilaurate and di-n-butyltin diacetate, di-n-butyltin oxide, dioctyltin diacetate, dioct Tyltin dilaurate, dioctyltin oxide, and also the reaction products of these compounds with alkoxysilanes and organo-functional alkoxysilanes such as tetraethoxysilane and aminopropyltriethoxysilane; The reaction product of di-n-butyltin dilaurate, dioctyltin dilaurate, tetraethyl silicate hydrolyzate and dibutyltin oxide and dioctyltin oxide or a reaction product of a hydrolyzate mixed with aminopropylsilane is preferred, and in particular It is preferably di-n-butyltin oxide in tetraethyl silicate hydrolyzate.

Preferably, when the composition of the present invention comprises an actual catalyst (F), in each case, based on 100 parts by weight of organopolysiloxane (A), preferably in an amount of 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight Is related to.

Preferred examples of the stabilizer (G) are phosphoric acid, phosphonic acid, phosphonic acid alkyl ester, and phosphoric acid alkyl ester.

Preferably, when the composition of the present invention actually contains a stabilizer (G), in each case based on 100 parts by weight of organopolysiloxane (A), preferably 0.01 to 100 parts by weight, more preferably 0.1 to 30 parts by weight , More particularly in an amount of 0.3 to 10 parts by weight.

Examples of additives (H) include pigments, dyes, odorants, oxidation inhibitors, agents that affect electrical properties, such as conductive carbon black, flame retardants, light stabilizers, disinfectants, heat stabilizers, scavengers, For example Si-N-containing silazane or silylamide, cocatalysts, thixotropic agents such as polyethylene glycol, polypropylene glycol or copolymers thereof, organic solvents such as alkyl aromatic compounds, paraffin oils, and also any different from component (A) Is a preferred siloxane.

Preferably, no organic solvent (H) is used in the preparation of the composition of the present invention.

When the composition of the present invention actually contains an additive (H), in each case, based on 100 parts by weight of organopolysiloxane (A), preferably 0.01 to 100 parts by weight, more preferably 0.1 to 30 parts by weight, more particularly Is related in an amount of 0.3 to 10 parts by weight.

Examples of the plasticizer (J) optionally used include dimethylpolysiloxane which is liquid at room temperature under a pressure of 1013 hPa and terminates with a trimethylsiloxy group, especially at 25° C. with a viscosity in the range of 20 to 5000 mPas; An organopolysiloxane that is liquid at room temperature under a pressure of 1013 hPa and is substantially composed of SiO _3/2 , SiO _2/2 and SiO _1/2 units referred to as T, D and M units; And also, for example, high-boiling hydrocarbons such as paraffinic oils or mineral oils composed substantially of naphthenic and paraffinic units.

The plasticizer (J) optionally used preferably comprises a linear polydimethylsiloxane having a trimethylsilyl end group.

When the composition of the present invention actually contains a plasticizer (J), in each case based on 100 parts by weight of organopolysiloxane (A), preferably 10 to 300 parts by weight, more preferably 10 to 1500 parts by weight, more In particular in amounts of 10 to 50 parts by weight. Preferably the composition of the present invention does not contain any plasticizer (J).

The composition of the present invention preferably,

(A) organopolysiloxane composed of units of formula (I),

(B) organosilicon compounds of formula (II) having at least one methyl or ethyl radical R ⁴ and/or partial hydrolyzates thereof,

(C) an organosilicon compound containing basic nitrogen and having the formula (III) and/or a partial hydrolyzate thereof,

(D) organosilicon compounds of formula (IV) having at least one ethyl radical R ⁸ and/or partial hydrolyzates thereof,

Optionally (E) a filler,

Optionally (F) a catalyst,

Optionally (G) a stabilizer,

Optionally (H) an additive and

Optionally (J) a composition comprising a plasticizer.

The composition of the present invention more preferably,

(A) an organopolysiloxane composed of units of formula (I) in which b and c are not zero in one or more units,

(B) organosilicon compounds of formula (II) having at least one methyl or ethyl radical R ⁴ and/or partial hydrolyzates thereof,

(C) an organosilicon compound containing basic nitrogen and having the formula (III) and/or a partial hydrolyzate thereof,

(D) organosilicon compounds of formula (IV) having at least one ethyl radical R ⁸ and/or partial hydrolyzates thereof,

Optionally (E) a filler,

Optionally (F) a catalyst,

Optionally (G) a stabilizer,

Optionally (H) an additive and

Optionally (J) a composition comprising a plasticizer.

The composition of the present invention is very preferably,

(A) organopolysiloxane of formula (V) wherein R ¹ is a vinyl radical,

(B) organosilicon compounds of formula (II) having at least one methyl or ethyl radical R ⁴ and/or partial hydrolyzates thereof,

(C) Formula (III) containing basic nitrogen and selected from N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyltriethoxysilane ) Having organosilicon compounds, and partial hydrolyzates thereof,

(D) an organosilicon compound of formula (IV) having an alkyl radical R ⁷ having 8 to 16 carbon atoms and at least one ethyl radical R ⁸ and/or a partial hydrolyzate thereof,

Optionally (E) a filler,

Optionally (F) a catalyst,

(G) a stabilizer,

Optionally (H) an additive and

(J) a composition containing a plasticizer,

However, the weight ratio of component (B) to component (C) is preferably in the range of 2:1 to 1:2.

The composition of the present invention more preferably,

(A) (MeO) ₂ MeSiO[SiMe ₂ O] _200-2000 SiVi(OMe) ₂ ,

(MeO) ₂ ViSiO[SiMe ₂ O] _200-2000 SiVi(OMe) ₂ ,

(MeO) ₂ MeSiO [SiMe ₂ O] _200-2000 SiViMe (OMe),

(MeO)ViMeSiO[SiMe ₂ O] _200-2000 SiViMe(OMe) and

(MeO)ViMeSiO[SiMe ₂ O] _200-2000 Organopolysiloxane selected from SiVi(OMe) ₂ compounds,

(B) tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenyltrimethoxysilane, An organosilicone compound selected from phenyltriethoxysilane and 1,2-bis(triethoxysilyl)ethane compound or a partial hydrolyzate thereof,

(C) an organosilicon containing basic nitrogen and selected from N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyltriethoxysilane Compounds and partial hydrolysates thereof,

(D) an organosilicone compound of formula (IV) having an alkyl radical R ⁷ having 8 to 16 carbon atoms and an ethyl radical R ⁸ and/or partial hydrolyzate thereof,

Optionally (E) a filler,

(F) catalyst,

(G) a stabilizer,

Optionally (H) an additive and

(J) a composition containing a plasticizer,

However, the weight ratio of component (B) to component (C) is preferably in the range of 2:1 to 1:2.

Additionally, in a more particularly preferred embodiment, the composition of the present invention,

(A) (MeO) ₂ MeSiO[SiMe ₂ O] _200-2000 SiVi(OMe) ₂ and

(MeO) ₂ ViSiO [SiMe ₂ O] _200-2000 SiVi (OMe) ₂ organopolysiloxane selected from the compound,

(B) an organosilicone compound selected from tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane compound, and a partial hydrolyzate thereof,

(C) an organosilicon containing basic nitrogen and selected from N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyltriethoxysilane Compounds and partial hydrolysates thereof,

(D) an organosilicone compound of formula (IV) having an alkyl radical R ⁷ having 8 to 16 carbon atoms and an ethyl radical R ⁸ and/or partial hydrolyzate thereof,

Optionally (E) a filler,

(F) catalyst,

(G) a stabilizer,

Optionally (H) an additive and

(J) a composition containing a plasticizer,

However, the weight ratio of component (B) to component (C) is preferably in the range of 2:1 to 1:2.

In another very particularly preferred embodiment, the composition of the invention,

(A) (MeO) ₂ ViSiO[SiMe ₂ O] _200-2000 SiVi(OMe) _2,

(B) vinyltriethoxysilane and/or partial hydrolyzate thereof,

(C) an organosilicon containing basic nitrogen and selected from N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyltriethoxysilane Compounds and partial hydrolysates thereof,

(D) organosilicon compounds of formula (IV) having n-octyl or isooctyl radicals R ⁷ and ethyl radicals R ⁸ and/or partial hydrolyzates thereof,

Optionally (E) a filler,

(F) catalyst,

(G) a stabilizer,

Optionally (H) an additive and

(J) a composition containing a plasticizer,

However, the weight ratio of component (B) to component (C) is preferably in the range of 3:2 to 2:3.

The composition of the present invention preferably contains no additional components other than components (A) to (J).

The composition of the present invention preferably contains, and more preferably does not contain, an organic solvent in an amount not exceeding 10 parts by weight, based on the total weight of the composition.

When the composition of the present invention actually contains a small amount of organic solvent, the organic solvent involved is preferably an alcohol formed in the hydrolysis and/or condensation reaction.

The individual components of the composition of the present invention may in each case comprise one such component or a mixture of two different such components.

The composition of the present invention comprises a liquid or viscous mixture, and is preferably a low-viscosity composition.

The composition of the present invention is measured according to DIN EN ISO 3219 using a plate/cone system at 25° C. and a shear rate of 25 1/s in each case, preferably less than 50,000 mPas, more preferably less than 25,000 mPas, and More particularly, it has a viscosity of less than 15,000 mPas.

The composition of the present invention can be prepared by mixing all the ingredients with each other in any order.

A further subject of the present invention relates to a method of preparing the composition of the present invention by mixing the individual components in any order.

This mixing can be carried out at room temperature under ambient atmospheric pressure, ie, about 900 to 1100 hPa. However, if desired, such mixing can also be carried out at higher temperatures, for example in the range from 35°C to 100°C. Furthermore, for example, in order to remove volatile compounds or air, mixing can be carried out intermittently or continuously under reduced pressure, for example under absolute pressure of 30 to 500 hPa.

Preferably, components (A), (B), (C), (D) and optionally a plasticizer (J), preferably trimethylsilyl-terminated organopolysiloxanes are mixed. This can be done at atmospheric pressure or under reduced pressure. Thereafter, it can be mixed in the filler (E), and dispersion can be carried out in the mixer at a relatively high rotational speed with relatively strong shear. This is generally carried out under reduced pressure to remove the reaction products of volatile compounds, air, and moisture of the filler and components (B) and (C). Additional components, such as stabilizers (G) or additives (H), may be added prior to or together with the filler (E). When the catalyst (F) is used, it is stirred evenly to the end. This is usually done under reduced pressure in order to render the liquid or low-viscosity composition inorganic.

The usual moisture content of air is sufficient to crosslink the composition of the present invention. Crosslinking of the composition of the present invention is preferably achieved at room temperature. If necessary, it can also be carried out at a temperature higher or lower than room temperature, for example -20°C to 15°C or 30°C to 60°C, and/or by a concentration of moisture in excess of the normal moisture content of the air have. Direct mixing of water or hydrous components is also possible.

The crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, more particularly at ambient atmospheric pressure, ie about 900 to 1100 hPa.

A further subject of the invention relates to moldings made by crosslinking the compositions of the invention.

The moldings of the invention are preferably coatings.

The composition of the present invention can be used for any purpose, and for this purpose, it can be stored with exclusion of moisture, and when water is allowed, it can be used as a composition that is crosslinked with an elastomer at room temperature.

The composition of the present invention is excellently suitable as a coating material for, for example, concrete, wood, steel, and aluminum. The coating can be applied by means of a brush or roller, or by spraying-for example by means of an airless spray. In this case, the sealing compound is applied directly to one layer, or to another layer on one, preferably with a layer thickness of 0.5 mm to 2 mm. Furthermore, they can be processed in a two-layer process with an embedded nonwoven web. The composition can be used either horizontally or vertically. The elastic protective coating is particularly resistant to exposure to sunlight, rain, fresh water or salt water. Moreover, the protective coating also has a high thermal stability.

The compositions of the present invention have the advantage that they are easy to manufacture and are distinguished by a very high storage stability.

In addition, the compositions of the present invention have the advantage that they have very good handling qualities during application and exhibit good processing properties for a wide range of applications.

In addition, the composition of the present invention has the advantage that it does not exhibit a relatively high shrinkage upon curing, especially compared to a formulation containing a solvent or other diluent.

The composition of the present invention has the advantage of curing effectively even under different climatic conditions. Thus, crosslinking is more independent of ambient temperature and atmospheric humidity. At the same time, a composition of the present invention with sufficient rapidity is one that may cause the composition to lose its sealing function, e.g., as a result of movement or shrinkage within the substrate, the partially vulcanized composition ruptures or Internal strength (cohesive force) to prevent foaming is developed.

Unless otherwise stated, the examples described below are at ambient atmospheric pressure, i.e., at about 1000 hPa, at room temperature, i.e. at about 23° C., and/or the temperature caused when the components are combined at room temperature without additional heating or cooling, And it is also carried out at a relative atmospheric humidity of about 50%. Also, unless stated otherwise, all numerical values for parts in percentage are parts by weight.

Skin-forming time (SFT) is measured on a foil applied with a thickness of 0.5 cm to 1 cm by contacting the surface at regular intervals at regular intervals using a freshly sharpened pencil of hardness HB. do. In this case, the time is recorded if no material is left hanging from the tip of the pencil as the fine skin is lifted by gradually raising the pencil. One day later, the quality of vulcanization is additionally examined based on the adhesion of the surface and the tear strength of the vulcanized material (fingernail test).

The measurement of viscosity and thixotropy is carried out on a rotary viscometer according to DIN EN ISO 3219. First, the viscosity is measured under high shear stress and then under low shear stress. The measurement is carried out by measuring urea CP25/2 in a plate/cone system at 25°C. Precondition for 1 minute at 0.5 1/s. It is then measured at 25 1/s for 1 minute and then 0.5 1/s for an additional 1 minute. It is evaluated as the average of 20 measurement points.

Mechanical values were measured according to ISO 37 on S2 specimens.

Shore A hardness was measured according to ISO 868.

Example 1

Dimethoxyvinylsilyl end group, 500 g of polydimethylsiloxane having a viscosity of 8,000 mPa·s, 3.0 g of an octylphosphonic acid mixture consisting of 25% by weight trimethoxymethylsilane and 75% by weight octylphosphonic acid, vinyltriethoxy 20 g of silane and 15 g of N-aminoethylaminopropyltrimethoxysilane are homogenized in a laboratory planetary mixer at about 300 rpm and a pressure of 200 to 300 hPa for 3 minutes. Then, 347 g of pulverized, uncoated marble powder having an average particle size of ² μm and 10 g of hydrophilic, pyrogenic silica having a specific surface area of 150 m ² /g were slowly mixed at a pressure of 900 to 1100 hPa, and 800 rpm And disperse for 8 minutes at a pressure of 200 to 300 hPa. The flowable mixture thus obtained was prepared by reaction of 1.4 g of di-n-butyltin oxide and 1.1 g of tetraethoxysilane for 3 minutes at 300 rpm and a pressure of 200 to 300 hPa and stirred to remove air bubbles, It was activated using 2.5 g of a tin catalyst and 100 g of isooctyltriethoxysilane.

A portion of the composition thus prepared was distributed to keep in the cartridge and stored for 24 hours at 23° C. and 50% relative atmospheric humidity before further testing, and another portion of the prepared composition was in an aluminum tube with an inside coating. Distributed and stored in a drying cabinet at 70 ℃ for 4 weeks.

Thereafter, the resulting composition was examined for skin-forming time and vulcanization as described above. The adhesiveness of the surface was tested on the back of the index finger or by a simple test using a finger. If the fingers are separated again without delay, the evaluation is positive. The results are shown in Table 1.

Example 2

The procedure described in Example 1 was repeated with the modification of using 100 g of isooctyltrimethoxysilane instead of isooctyltriethoxysilane.

The results are shown in Table 1.

Example 3

The procedure described in Example 1 was repeated with the modification of using 100 g of hexadecyltrimethoxysilane instead of isooctyltriethoxysilane.

The results are shown in Table 1.

Comparative Example C1

The procedure described in Example 1 was repeated with a modification using 100 g of isoparaffin hydrocarbons (flash point> 90°C, viscosity 3.5 cSt/25°C) as a solvent instead of isooctyltriethoxysilane.

The results are shown in Table 1.

Example One 2 3 C1
Paste properties SFT [min] after 24 hours storage 10 18 15 7 SFT [min] after 4 weeks/70℃ storage 13 22 20 10 Surface after curing for 24 hours positivity positivity positivity positivity Vulcanized material after curing for 24 hours positivity Slightly fragile positivity positivity
Viscosity / 25℃ [mPas] Shear rate 25 1/s 8　000 7　500 8　500 8　000 Shear rate 25 1/s 27　000 26　000 27　000 34　000

SFT = skin-forming time

Example 4

Dimethoxyvinylsilyl end group, 500 g of polydimethylsiloxane having a viscosity of 8,000 mPa·s, 3.0 g of an octylphosphonic acid mixture consisting of 25% by weight trimethoxymethylsilane and 75% by weight octylphosphonic acid, vinyltriethoxy 20 g of silane and 15 g of N-aminoethylaminopropyltrimethoxysilane are homogenized in a laboratory planetary mixer at about 300 rpm and a pressure of 200 to 300 hPa for 3 minutes. Then, 347 g of pulverized, uncoated marble powder having an average particle size of ² μm and 10 g of hydrophilic, pyrogenic silica having a specific surface area of 150 m ² /g were slowly mixed at a pressure of 900 to 1100 hPa, and 800 rpm And disperse for 8 minutes at a pressure of 200 to 300 hPa. The flowable mixture thus obtained was prepared by reaction of 0.9 g of di-n-octyltin oxide and 2.1 g of tetraethoxysilane for 3 minutes at 300 rpm and a pressure of 200 to 300 hPa and stirred to remove air bubbles, It was activated using 5.0 g of tin catalyst and 50 g of isooctyltriethoxysilane.

The composition thus prepared was dispensed into a cartridge, as described in Example 1.

The resulting composition was then examined for skin-forming time, vulcanization, and surface tack as described above.

In addition, the composition was crosslinked for 14 days at 23° C. and 50% relative atmospheric humidity, and mechanical properties and Shore hardness were measured according to ISO 37 and ISO 868, respectively. The results are shown in Table 2.

Example 5

The procedure described in Example 4 was repeated with the modification of mixing 100 g of isooctyltriethoxysilane instead of 50 g of isooctyltriethoxysilane.

The results are shown in Table 2.

Example 6

The procedure described in Example 4 was repeated with the modification of mixing 200 g of isooctyltriethoxysilane instead of 50 g of isooctyltriethoxysilane.

The results are shown in Table 2.

Comparative Example C2

The procedure described in Example 4 was repeated with the modification of not mixing isooctyltriethoxysilane.

The results are shown in Table 2.

Comparative Example C3

The procedure described in Example 4 was repeated with the modification of mixing 100 g of tetraethoxysilane with the catalyst instead of isooctyltriethoxysilane.

The results are shown in Table 2.

Comparative Example C4

The procedure described in Example 4 was repeated with the modification of mixing 100 g of oligomerized tetraethoxysilane having a SiO ₂ content of about 40% by weight in place of isooctyltriethoxysilane with the catalyst.

The results are shown in Table 2.

Example 4 5 6 C2 C3 C4
Paste properties SFT [min] after 24 hours storage 8 8 8 8 15 15 Surface after curing for 24 hours positivity positivity positivity positivity voice
Sticky voice
Sticky Vulcanized material after curing for 24 hours positivity positivity positivity positivity voice
Fragility voice
Not cured
Viscosity / 25°C [mPas] Shear rate
25 1/s 14　500 8　500 3　000 28　000 7　000 12　000 Shear rate 25 1/s 48　000 30　000 10　000 100　000 27　000 50　000
Mechanical properties of the foil according to ISO 37-S2 Shore A 42 41 27 48 47 n.m. TS-MPa 1.9 1.5 1.5 2.0 1.5 n.m. EB-% 140 150 160 120 60 n.m.

SFT = skin-forming time

TS = tensile strength

EB = elongation at break

n.m. = Not measurable

Claims (11)

(A) Organopolysiloxane containing an organyloxy group and composed of units of the following formula (I):
R _a R ¹ _b (OR ² ) _c SiO _(4-abc)/2 (I),
(Wherein, R may be the same or different and represent a monovalent, SiC-bonded, optionally substituted hydrocarbyl radical without aliphatic carbon-carbon multiple bonds,
R ¹ may be the same or different and represents a monovalent, SiC-bonded, optionally substituted hydrocarbyl radical having aliphatic carbon-carbon multiple bonds,
R ² may be the same or different and represent a monovalent, optionally substituted hydrocarbyl radical, which may be interrupted by an oxygen atom,
a is 0, 1, 2 or 3,
b is 0 or 1,
c is 0, 1, 2 or 3,
However, in formula (I), the sum of a+b+c is 3 or less, and c is not 0 in one or more units),
(B) the organosilicon compound of the following formula (II) and/or a partial hydrolyzate thereof:
(R ⁴ O) _d SiR ³ _(4-d) (II),
(Wherein, R ³ may be the same or different and optionally have 1 to 7 carbon atoms substituted by an ether group, an ester group, a (poly) glycol radical or a triorganyloxysilyl group, a monovalent, SiC- Represents a bonded, aliphatic hydrocarbyl radical or an aromatic radical,
R ⁴ may be the same or different and represent a hydrogen atom or represent a monovalent, optionally substituted hydrocarbyl radical, which may be interrupted by an oxygen atom,
d is 2, 3 or 4),
(C) an organosilicon compound containing basic nitrogen and having the following formula (III) and/or a partial hydrolyzate thereof:
(R ⁶ O) _e SiR ⁵ _(4-e) (III),
(Wherein, R ⁵ may be the same or different and represent a monovalent, SiC-bonded radical containing a basic nitrogen,
R ⁶ may be the same or different and represent a hydrogen atom or represent a monovalent, optionally substituted hydrocarbyl radical, which may be interrupted by an oxygen atom,
e is 2 or 3), and
(D) organosilicon compound of the following formula (IV) and/or partial hydrolyzate thereof
(R ⁸ O) _h SiR ⁷ _(4-h) (IV),
(Wherein, R ⁷ may be the same or different, optionally substituted by an ether group, an ester group, a (poly) glycol radical or a triorganyloxysilyl group, and having 8 or more carbon atoms, a monovalent, SiC-bond Represents an aliphatic hydrocarbyl radical,
R ⁸ may be the same or different and represent a hydrogen atom or represent a monovalent, optionally substituted hydrocarbyl radical, which may be interrupted by an oxygen atom,
h is 2 or 3)
Crosslinkable composition comprising a. The method of claim 1, wherein the organopolysiloxane (A) is represented by the following formula (V):
(OR ² ) _3-f R ¹ _f Si-(SiR ₂ -O) _g -SiR ¹ _f (OR ² ) _3-f (V)
(In the formula, R, R ¹ and R ² may each be the same or different, and have one of the definitions described above,
g is 30 to 5000,
f is 0, 1 or 2,
However, in equation (V), f is not 0 in one or more units)
A crosslinkable composition that is a substantially linear, organyloxy terminated organopolysiloxane of. The organopolysiloxane (A) according to claim 1 or 2,
(MeO) ₂ MeSiO[SiMe ₂ O] _200-2000 SiMe(OMe) ₂ ,
(MeO) ₂ MeSiO[SiMe ₂ O] _200-2000 SiVi(OMe) ₂ ,
(MeO) ₂ ViSiO[SiMe ₂ O] _200-2000 SiVi(OMe) ₂ ,
(MeO) ₂ MeSiO [SiMe ₂ O] _200-2000 SiViMe (OMe),
(MeO)ViMeSiO[SiMe ₂ O] _200-2000 SiViMe(OMe) or
(MeO)ViMeSiO[SiMe ₂ O] _200-2000 SiVi(OMe) _{2 The} crosslinkable composition. The crosslinkable composition according to any one of claims 1 to 3, wherein the organosilicone compound (D) has at least one radical R ⁸ having at least 2 carbon atoms. The method according to any one of claims 1 to 4, wherein the organosilicone compound (D) is hexadecyltrimethoxysilane, hexadecyltriethoxysilane, n-octyltrimethoxysilane, and n-octyltriethoxy A crosslinkable composition which is silane, isooctyltrimethoxysilane or isooctyltriethoxysilane and/or a partial hydrolyzate thereof. The crosslinkable composition according to any one of claims 1 to 5, wherein the weight ratio of component (B) to component (C) is 2:1 to 1:2. The method according to any one of claims 1 to 6,
(A) organopolysiloxane composed of units of formula (I),
(B) organosilicon compounds of formula (II) having at least one methyl or ethyl radical R ⁴ and/or partial hydrolyzates thereof,
(C) an organosilicon compound containing basic nitrogen and having the formula (III) and/or a partial hydrolyzate thereof,
(D) organosilicon compounds of formula (IV) having at least one ethyl radical R ⁸ and/or partial hydrolyzates thereof,
Optionally (E) a filler,
Optionally (F) a catalyst,
Optionally (G) a stabilizer,
Optionally (H) an additive, and
Optionally (J) a crosslinkable composition comprising a plasticizer. The method according to any one of claims 1 to 7,
(A) organopolysiloxane of formula (V) having a vinyl radical R ¹ ,
(B) organosilicon compounds of formula (II) having at least one methyl or ethyl radical R ⁴ and/or partial hydrolyzates thereof,
(C) contains basic nitrogen and is selected from N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and formula (III) ) Having organosilicon compounds and partial hydrolyzates thereof,
(D) an organosilicon compound of formula (IV) having an alkyl radical R ⁷ having 8 to 16 carbon atoms and at least one ethyl radical R ⁸ and/or a partial hydrolyzate thereof,
Optionally (E) a filler,
Optionally (F) a catalyst,
(G) a stabilizer,
Optionally (H) an additive, and
(J) contains a plasticizer,
However, the weight ratio of component (B) to component (C) is preferably in the range of 2:1 to 1:2. A method for preparing a crosslinkable composition according to any one of claims 1 to 8, comprising:
A method comprising mixing all of the ingredients with each other in any order. A molded article produced by crosslinking the composition according to any one of claims 1 to 8. The molding according to claim 10, which is a coating.